CN108164547B - Poly-fused ring conjugated macromolecule and preparation method and application thereof - Google Patents
Poly-fused ring conjugated macromolecule and preparation method and application thereof Download PDFInfo
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- 229920002521 macromolecule Polymers 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 126
- 239000000463 material Substances 0.000 claims abstract description 53
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 281
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 80
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- -1 C1-C20 alkylthio Chemical group 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 125000004414 alkyl thio group Chemical group 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 229930192474 thiophene Natural products 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 238000006482 condensation reaction Methods 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 150000007514 bases Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000003367 polycyclic group Chemical group 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 73
- 239000000203 mixture Substances 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- 239000000741 silica gel Substances 0.000 description 39
- 229910002027 silica gel Inorganic materials 0.000 description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 229920003026 Acene Polymers 0.000 description 23
- 238000002484 cyclic voltammetry Methods 0.000 description 22
- 238000000862 absorption spectrum Methods 0.000 description 21
- 239000003480 eluent Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 18
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 230000008033 biological extinction Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000004770 highest occupied molecular orbital Methods 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
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- 239000010981 turquoise Substances 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 238000013375 chromatographic separation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- UFFXQKZAZJAMCH-UHFFFAOYSA-N 4-fluoroindene-1,3-dione Chemical compound FC1=CC=CC2=C1C(=O)CC2=O UFFXQKZAZJAMCH-UHFFFAOYSA-N 0.000 description 1
- OTNMXNJAYRIKQO-UHFFFAOYSA-N 5-fluoroindene-1,3-dione Chemical compound FC1=CC=C2C(=O)CC(=O)C2=C1 OTNMXNJAYRIKQO-UHFFFAOYSA-N 0.000 description 1
- HDMHJXOJLIYDFU-UHFFFAOYSA-N FC1=C(F)C=C2C(=O)CC(=O)C2=C1 Chemical compound FC1=C(F)C=C2C(=O)CC(=O)C2=C1 HDMHJXOJLIYDFU-UHFFFAOYSA-N 0.000 description 1
- 241000607059 Solidago Species 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the field of solar cells, in particular to a poly-fused ring conjugated macromolecule and a preparation method and application thereof. The poly-fused ring conjugated macromolecule is one of a compound shown in a formula (1F) and a compound shown in a formula (1). The poly-fused ring conjugated macromolecule provided by the invention has stronger light absorption, higher charge transmission performance and proper electron energy level, and is suitable for being used as an electron donor or electron acceptor material to be applied to the preparation of solar cells.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a poly-fused ring conjugated macromolecule and a preparation method and application thereof.
Background
In recent years, organic solar cells have been rapidly developed, and have received much attention from academia and industry due to their advantages of light weight, good flexibility, simple processing method, large-area preparation, and low cost. At present, the photoelectric conversion efficiency of solar cells prepared based on blending of polymer donors and fullerene receptors has broken through by 11%. This shows a great application prospect for organic solar cells. The polymer material has higher photoelectric conversion efficiency of the photovoltaic device due to higher molar extinction coefficient and wider solar spectrum absorption. However, polymers also have disadvantages, such as: uncertain molecular structure, polydispersity molecular weight distribution, difficult batch repeatability, difficult purification and the like. Different from polymers, organic condensed ring micromolecules and macromolecular semiconductor materials have the advantages of determined molecular structures and molecular weights, stable batches, simplicity in purification, high purity and the like, so that the research of organic condensed ring micromolecules and macromolecular solar cells tends to be hot.
Due to the advantages of the fullerene derivative such as enough electron affinity, isotropic electron transport performance, relatively matched electron energy level and the like, the fullerene derivative (PC)61BM and PC71BM) become star molecules in the receptor material and always dominateAnd (5) a position. However, PCBM also has many disadvantages, such as weak visible light absorption, difficult energy level regulation, complex and tedious purification process, and the like. Therefore, the synthesis of novel receptor materials is still necessary.
Disclosure of Invention
The invention aims to provide a novel multi-fused ring conjugated macromolecule which can be used for a solar cell as an electron donor or electron acceptor material and has stronger light absorption, higher charge transmission performance and proper electron energy level, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a multiple fused ring conjugated macromolecule, which is a compound represented by the following formula (1F):
formula (1F)
Wherein each group
Each independently represents 1 to 10 thiophene conjugated fused ring structures;
each group A is independently selected from one of the groups shown in the following formulas:
wherein R is3-R6At least one of which is F, the others are each independently selected from H, alkyl, alkoxy and alkylthio; wherein each R is1Each independently selected from the group consisting of
A group shown and formula
A group shown; each R is2Each independently selected from the group consisting of
Shown inA group; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O, S and Se; m is an integer of 0 to 6; p is an integer of 0 to 6; n is an integer of 0 to 6; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C12 aryl.
The invention also provides a preparation method of the poly-fused ring conjugated macromolecule, which comprises the following steps:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1F); wherein the content of the first and second substances,
formula (2)
Formula (a)
The invention also provides a poly-fused ring conjugated macromolecule, which is a compound shown in the following formula (1):
formula (1)
Wherein each group
Each independently represents 3 to 10 thiophene conjugated fused ring structures;
each group A' is independently selected from one of the groups represented by the following formulas:
wherein R is3-R6Each independently selected from H, alkyl, alkoxy, and alkylthio; wherein each R is1Each independently selected from the group consisting of
A group shown and formula
A group shown; each R is2Each independently selected from the group consisting of
A group shown; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O, S and Se; m is an integer of 0 to 6; p is an integer of 0 to 6; n is an integer of 0 to 6; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C12 aryl.
The invention also provides a preparation method of the poly-fused ring conjugated macromolecule, which comprises the following steps:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a') to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein the content of the first and second substances,
formula (2)
Formula (a')
The invention also provides a photovoltaic material containing one or more of the poly-fused ring conjugated macromolecules.
The invention also provides a solar cell which comprises a light-trapping active layer, wherein the electron donor material and/or the electron acceptor material in the light-trapping active layer contain one or more of the poly-fused ring conjugated macromolecules.
The invention also provides a preparation method of the solar cell, wherein the method comprises the step of using an electron donor material and/or an electron acceptor material containing one or more of the multi-fused ring conjugated macromolecules to form a light-trapping active layer.
The poly-fused ring conjugated macromolecule provided by the invention has stronger light absorption, higher charge transmission performance and proper electron energy level, is suitable for being used as an electron donor or electron acceptor material to be applied to the preparation of solar cells, and particularly can obtain the solar cells with the photoelectric conversion efficiency of 10-12%.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows UV-VIS absorption spectra of a polycyclic conjugated macromolecule represented by the formula (1F-5-F1) obtained in example 1 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 2 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-5-F1) obtained in example 1 of the present invention.
FIG. 3 shows UV-VIS absorption spectra of a poly-fused ring conjugated macromolecule represented by formula (1F-5-F2) obtained in example 2 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 4 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-5-F2) obtained in example 2 of the present invention.
FIG. 5 shows an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1F-5-13) obtained in example 3 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 6 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-5-13) obtained in example 3 of the present invention.
FIG. 7 shows UV-VIS absorption spectra of a poly-fused ring conjugated macromolecule represented by formula (1F-7-F1) obtained in example 4 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 8 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-7-F1) obtained in example 4 of the present invention.
FIG. 9 shows UV-VIS absorption spectra of poly-fused ring conjugated macromolecules represented by formula (1F-7-F3) obtained in example 5 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 10 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-7-F3) obtained in example 5 of the present invention.
FIG. 11 is an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1F-7-15) obtained in example 6 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 12 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-7-15) obtained in example 6 of the present invention.
FIG. 13 is a UV-VIS absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1F-9-F1) prepared in example 7 according to the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 14 is a cyclic voltammogram of a polyatomic fused ring conjugated macromolecule represented by formula (1F-9-F1) obtained in example 7 of the present invention.
FIG. 15 shows an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1F-9-2) obtained in example 8 of the present invention, wherein the solution is represented bySolution (10) with chloroform as solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 16 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-9-2) obtained in example 8 of the present invention.
FIG. 17 shows an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1F-9-14) obtained in example 9 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 18 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1F-9-14) obtained in example 9 of the present invention.
FIG. 19 is an ultraviolet-visible absorption spectrum of a polycyclic conjugated macromolecule represented by the formula (1-9-2) obtained in example 10 of the present invention, wherein the solution is a solution (10) prepared using chloroform as a solvent-6mol/L) of the film is a film (100 nm in thickness) formed by spin coating chloroform solution.
FIG. 20 is a cyclic voltammogram of a poly-fused ring conjugated macromolecule represented by formula (1-9-2) obtained in example 10 of the present invention.
FIG. 21 is an I-V curve of the solar cell obtained in example 13. FIG. 22 is an I-V curve of the solar cell obtained in example 14. FIG. 23 is an I-V curve of the solar cell obtained in example 15. FIG. 24 is an I-V curve of the solar cell obtained in example 16. FIG. 25 is an I-V curve of the solar cell obtained in example 17. FIG. 26 is an I-V curve of the solar cell obtained in example 18. FIG. 27 is an I-V curve of a solar cell obtained in example 19. FIG. 28 is an I-V curve of the solar cell obtained in example 20. FIG. 29 is an I-V curve of the solar cell obtained in example 21. FIG. 30 is an I-V curve of a solar cell obtained in example 22. FIG. 31 is an I-V curve of a solar cell obtained in example 23. FIG. 32 is an I-V curve of a solar cell obtained in example 24.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, each group is independently selected from the group represented, and when each group occurs simultaneously and at multiple positions in the compound, they are independently selected, may be the same, or may be different, for example, although
Having two R in the group shown7However, the two R7Are independently selectable, and may be the same or different.
In the present invention,
the dashed lines in the structures with dashed connecting bonds indicate the connecting sites and indicate the connecting bonds;
the solid line in the structure with the solid line connecting bond not connecting any group or atom also indicates the connecting site, representing the connecting bond.
In the present invention, the composition contains
The groups are such that F is taken on both the left and right sides of the bond through which-F is inserted, for example, the following formula (1F-5-F1) means in fact that the formula (1F-5-5) in which the groups A on both sides are the groups A-2, the formula (1F-5-8) in which the groups A on both sides are the groups A-3, and the groups A on both sides are one group A-3 and the other group AA mixture of compounds represented by the formula (1F-5-35) each being a group A-2.
The invention provides a poly-fused ring conjugated macromolecule, which is a compound shown in the following formula (1F):
formula (1F)
Wherein each group
Each independently represents 1 to 10 thiophene conjugated fused ring structures;
each group A is independently selected from one of the groups shown in the following formulas:
wherein R is3-R6At least one of which is F, the others are each independently selected from H, alkyl, alkoxy and alkylthio; wherein each R is1Each independently selected from the group consisting of
The radicals shown (preferably)
) And formula
A group shown; each R is2Each independently selected from the group consisting of
The radicals shown (preferably)
) (ii) a Each Z is independently selected from C, N and Si; each X and each Y is independently selected from O, S and Se; m is an integer of 0 to 6; p is an integer of 0 to 6; n is an integer of 0 to 6; each R is7Each R8Each of themR is9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C20 alkylthio, and C6-C12 aryl.
According to the present invention, in order to obtain a conjugated macromolecule having stronger light absorption, higher charge transport property and more suitable electron energy level, it is preferable that each group
Each independently represents 1 to 5 thiophene conjugated fused ring structures; r3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O and S; m is an integer of 0 to 4; p is an integer of 0 to 4; n is an integer of 0 to 4; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, and C6-C10 aryl.
More preferably, each group
Each independently represents 1 to 4 thiophene conjugated fused ring structures; r3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, and C1-C20 alkylthio; each Z is independently selected from C and N; each R is7Each R9And each R11Each independently selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 alkylthio; each R is8And each R10And each independently selected from the group consisting of H, C4-C10 alkyl, C4-C10 alkoxy, and C4-C10 alkylthio.
Even more preferably, R3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C10 alkyl, C1-C10 alkoxy, and C1-C10 alkylthio; each Z is independently selected from C and N; m is 0, 1, 2 or 3; p is 0, 1, 2 or 3; n is 0, 1, 2 or 3; each one ofR is7Each R9And each R11Each independently selected from H, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio, and n-butylthio; each R is8And each R10And each is independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
Where n is 0, R can be considered to be2When the substituent is absent, the group A is directly bonded to the fused ring unit main body of the compound represented by the formula (1F) to form a conjugated structure. Specific examples of the alkyl group having C1 to C10 may be, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, and the like. Alkyl groups within other ranges of the present invention may also be selected from the specific examples as appropriate. Specific examples of the alkoxy group having C1 to C10 include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, 2-ethylhexoxy and the like. The alkoxy group in the other ranges of the present invention can be selected from the specific examples as appropriate. Specific examples of the alkylthio group having from C1 to C10 include, for example: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, 2-ethylhexylthio and the like. Specific examples of the aryl group having C6 to C10 may be, for example: phenyl, benzyl, p-tolyl, and the like.
Wherein, two groups located at both sides of the conjugated structure in the middle of the compound (1F)
It is to be understood as being co-centered with the compound (1F)The yoke structures together form a conjugated structure, wherein the yoke structures respectively and independently represent 1-10 thiophene conjugated condensed ring structures, and when the group B is 1 thiophene conjugated condensed ring structure, actually, 1 thiophene group and the middle conjugated structure at two sides form a basic structure of a conjugated macromolecule.
Preferably, the conjugated macromolecule is one of the compounds shown in the following formula:
formula (1F-5):
(corresponding to 1 thiophene conjugated condensed ring structure in all groups B); formula (1F-7):
(corresponding to 2 thiophene conjugated condensed ring structures in all groups B); formula (1F-9):
(corresponding to 3 thiophene conjugated condensed ring structures in all groups B); formula (1F-11):
(corresponding to 4 thiophene conjugated condensed ring structures in all groups B).
According to the invention, the group A has a strong electron pulling effect, and the group A is positioned at two ends of a condensed ring unit, so that the obtained conjugated macromolecule has strong visible light absorption capacity, high charge transmission performance and proper electron energy level, and is suitable for being used as an electron donor or electron acceptor material to be applied to preparing an organic solar cell.
Preferably, the group a is selected from one or more of the following groups:
the radical A-1 is
The group A-2 is
The radical A-3 is
The group A-4 is
The radical A-5 is
The radical A-6 is
The radical A-7 is
The radical A-8 is
The radical A-9 is
The radical A-10 is
The radical A-11 is
According to the present invention, the polyacene ring conjugated macromolecule of the present invention is preferably one of the compounds represented by the following formula:
formula (1F-5-1): in the formula (1F-5), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl; formula (1F-5-2): in the formula (1F-5), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-3): in the formula (1F-5), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-4): formula (1F-5) Wherein Z is C, A is a group A-2, R2Is absent, R1Are both n-hexyl; formula (1F-5-5): in the formula (1F-5), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-6): in the formula (1F-5), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-7): in the formula (1F-5), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl; formula (1F-5-8): in the formula (1F-5), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-9): in the formula (1F-5), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-10): in the formula (1F-5), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl; formula (1F-5-11): in the formula (1F-5), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-12): in the formula (1F-5), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-13): in the formula (1F-5), Z is C, A is A-5, R2Is absent, R1Are both n-hexyl;formula (1F-5-14): in the formula (1F-5), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-15): in the formula (1F-5), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-16): in the formula (1F-5), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl; formula (1F-5-17): in the formula (1F-5), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-18): in the formula (1F-5), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-19): in the formula (1F-5), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl; formula (1F-5-20): in the formula (1F-5), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-21): in the formula (1F-5), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-22): in the formula (1F-5), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl; formula (1F-5-23): in the formula (1F-5), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-24): in the formula (1F-5), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-25): in the formula (1F-5), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl; formula (1F-5-26): in the formula (1F-5), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-27): in the formula (1F-5), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-28): in the formula (1F-5), Z is C, A is A-10, R2Is absent, R1Are both n-hexyl; formula (1F-5-29): in the formula (1F-5), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-30): in the formula (1F-5), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-31): in the formula (1F-5), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl; formula (1F-5-32): in the formula (1F-5), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-33): in the formula (1F-5), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-5-34): in the formula (1F-5), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl; formula (1F-5-35): in the formula (1F-5), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-5-36): in the formula (1F-5), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-1): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl; formula (1F-7-2): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-3): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-4): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl; formula (1F-7-5): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-6): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-7): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl; formula (1F-7-8): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-9): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-10): in the formula (1F-7), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl; formula (1F-7-11): in the formula (1F-7), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-12): (1F-7) wherein Z is C and A is a group A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-13): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are both n-hexyl; formula (1F-7-14): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl(ii) a Formula (1F-7-15): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-16): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl; formula (1F-7-17): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-18): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-19): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl; formula (1F-7-20): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-21): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-22): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl; formula (1F-7-23): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-24): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-25): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl; formula (1F-7-26): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-27): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-28): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are both n-hexyl; formula (1F-7-29): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-30): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-31): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl; formula (1F-7-32): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-33): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-7-34): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl; formula (1F-7-35): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-7-36): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-1): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl; formula (1F-9-2): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-3): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-4): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl; formula (1F-9-5): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-6): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-7): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl; formula (1F-9-8): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-9): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-10): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl; formula (1F-9-11): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-12): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-13): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are both n-hexyl; formula (1F-9-14): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-15): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-16): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl; formula (1F-9-17): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-18): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-19): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl; formula (1F-9-20): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-21): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-22): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl; formula (1F-9-23): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-24): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-25): in the formula (1F-9), Z is C, A is A-9, R2Is absent from，R1Are both n-hexyl; formula (1F-9-26): in the formula (1F-9), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-27): in the formula (1F-9), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-28): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are both n-hexyl; formula (1F-9-29): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-30): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-31): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl; formula (1F-9-32): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-33): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-9-34): in the formula (1F-9), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl; formula (1F-9-35): formula (1F-9)Wherein Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-9-36): in the formula (1F-9), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-1): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl; formula (1F-11-2): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-3): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-4): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl; formula (1F-11-5): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-6): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-7): in the formula (1F-11), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl; formula (1F-11-8): formula (1)F-11), Z is C, A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-9): in the formula (1F-11), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-10): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl; formula (1F-11-11): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-12): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-13): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are both n-hexyl; formula (1F-11-14): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-15): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-16): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl; formula (1F-11-17): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-18): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-19): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl; formula (1F-11-20): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-21): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-22): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl; formula (1F-11-23): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-24): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-25): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl; formula (1F-11-26): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-27): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-28): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are both n-hexyl; formula (1F-11-29): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-30): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-31): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl; formula (1F-11-32): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-33): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1F-11-34): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl; formula (1F-11-35): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1F-11-36): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl.
The invention also provides a preparation method of the poly-fused ring conjugated macromolecule, which comprises the following steps:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1F); wherein the content of the first and second substances,
formula (2)
Formula (a)
In the method, the group
R1-R6As described above, the present invention is not described in detail herein.
Wherein, the compound shown in the formula (2) can be selected according to the structure of the poly-fused ring conjugated macromolecule, preferably, the compound shown in the formula (2) is one or more of the following formulas:
formula (2-5)
Formula (2-7)
Formula (2-9):
formula (2-11):
specific examples of the compound represented by the formula (2) may be, for example, one or more of the following formulae:
formula (2-5-1): in the formula (2-5), Z is C or R2Is absent, R1Are both n-hexyl; formula (2-5-2): in the formula (2-5), Z is C or R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (2-5-3): in the formula (2-5), Z is C or R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (2-7-1): in the formula (2-7), Z is C or R2Is absent, R1Are both n-hexyl; formula (2-7-2): in the formula (2-7), Z is C or R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (2-7-3): in the formula (2-7), Z is C or R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (2-9-1): in the formula (2-9), Z is C or R2Is absent, R1Are both n-hexyl; formula (2-9-2): in the formula (2-9), Z is C or R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (2-9-3): in the formula (2-9), Z is C or R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (2-11-1): in the formula (2-11), Z is C or R2Is absent, R1Are both n-hexyl; formula (2-11-2): in the formula (2-11), Z is C or R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (2-11-3): in the formula (2-11), Z is C or R2Is absent, R1Are all made of
And R is8Is n-hexyl.
According to the present invention, the compound represented by the formula (2) may be a commercially available product, or may be prepared by a method conventional in the art, for example, by reacting an aldehyde group with butyllithium (for example, by a method described in Adv. Mater.,2015,27, 1170-1174; J.Am. chem. Soc.,2016,138,4955-4961, etc.).
According to the present invention, the compound represented by the formula (a) may be appropriately selected according to the group a, and for example, specific examples of the compound represented by the formula (a) may include:
formula (a-1):
formula (a-2):
formula (a-3):
formula (a-4):
formula (a-5):
formula (a-6):
formula (a-7):
formula (a-8):
formula (a-9):
formula (a-10):
formula (a-11):
according to the present invention, the compound represented by formula (a) may be a commercially available product or may be prepared by a method conventional in the art, and will not be described herein again.
According to the present invention, the aldehyde group connected to both ends of the compound represented by formula (2) can be subjected to dehydration condensation with the compound represented by formula (a) to form the compound represented by formula (1F), wherein the amount of the compound represented by formula (2) and the compound represented by formula (a) used is not particularly limited as long as the compound represented by formula (1F) can be obtained, and preferably, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a) is 1: 2-100, more preferably 1: 4-10.
According to the present invention, the reaction is carried out in the presence of a basic compound, which may be, for example, one or more of piperidine, pyridine and triethylamine, thereby making it possible to provide a basic environment to the reaction system. The amount of the basic compound to be used is not particularly limited as long as it can provide a basic environment and contribute to the progress of the dehydration condensation reaction, and is, for example, 0.1 to 1000mmol, more preferably 1 to 50mmol, relative to 1mmol of the compound represented by formula (2).
According to the invention, the organic solvent is, for example, chloroform and/or dichloromethane. The amount of the organic solvent to be used may be, for example, 20 to 500mL (preferably 40 to 400mL) per 1mmol of the compound represented by the formula (2).
According to the present invention, preferably, the dehydration condensation reaction conditions include: the temperature is 20-100 deg.C (such as 50-100 deg.C), and the time is 10min-48h (such as 10-20 h). More preferably, the conditions of the dehydration condensation reaction include: the temperature is 60-80 ℃ and the time is 10-15 h.
In order to ensure the smooth proceeding of the reaction, the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after all the raw materials are added, the non-reactive gas may be introduced into the reaction system for 20-40min to remove air. The inert gas may be, for example, argon, helium, nitrogen, or the like.
According to the present invention, in order to extract the compound represented by the formula (1F) from the reaction solution, the method further comprises a post-treatment step, for example, mixing the dehydration condensation reaction product with methanol (the amount of methanol may be, for example, 200-1000mL relative to the total volume of 100mL of the reaction solution), then carrying out solid-liquid separation, and carrying out chromatographic separation on the obtained solid phase by using a silica gel chromatographic column (200-300 mesh silica gel may be used, and the eluent may be a mixed solution of petroleum ether and dichloromethane in a volume ratio of 1: 0.2-3).
The invention also provides a poly-fused ring conjugated macromolecule, which is a compound shown in the following formula (1):
formula (1)
Wherein each group
Each independently represents 3 to 10
A thiophene conjugated fused ring structure; each group A' is independently selected from one of the groups represented by the following formulas:
wherein R is3-R6Each independently selected from H, alkyl, alkoxy, and alkylthio; wherein each R is1Each independently selected from the group consisting of
A group shown and formula
A group shown; each R is2Each independently selected from the group consisting of
A group shown; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O, S and Se; m is an integer of 0 to 6; p is an integer of 0 to 6; n is an integer of 0 to 6; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C12 aryl.
According to the invention, the groups in the polya-fused ring conjugated macromolecule may be chosen from those described above, for which reason the invention is not described again for each group.
Wherein, preferably, each group
Each independently represents 3 to 5 thiophene conjugated fused ring structures; r3-R6Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O and S; m is an integer of 0 to 4; p is an integer of 0 to 4; n is an integer of 0 to 4; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, and C6-C10 aryl.
More preferably, each group
Each independently represents 3 to 4 thiophene conjugated fused ring structures; r3-R6Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, and C1-C20 alkylthio; each Z is independently selected from C and N; each R is7Each R9And each R11Each independently selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 alkylthio; each R is8And each R10And each independently selected from the group consisting of H, C4-C10 alkyl, C4-C10 alkoxy, and C4-C10 alkylthio.
Even more preferably, R3-R6Each independently selected from the group consisting of H, C1-C10 alkyl, C1-C10 alkoxy, and C1-C10 alkylthio; each Z is independently selected from C and N; m is 0, 1, 2 or 3; p is 0, 1, 2 or 3; n is 0, 1, 2 or 3; each R is7Each R9And each R11Each independently selected from H, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio, and n-butylthio; each R is8And each R10And each is independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
Preferably, the multiple fused ring conjugated macromolecule is one of the compounds shown in the following formula:
formula (1-9):
(corresponding to 3 thiophene conjugated condensed ring structures in all groups B);
formula (1-11):
(corresponding to 4 thiophene conjugated condensed ring structures in all groups B). Preferably, the group A 'is a group A' -1
According to the present invention, a specific example of the above-mentioned polyacondensed ring conjugated macromolecule may be one of compounds represented by the following formulae:
formula (1-9-1): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are both n-hexyl; formula (1-9-2): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1-9-3): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is8Is n-hexyl; formula (1-11-1): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are both n-hexyl; formula (1-11-2): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is10Is n-hexyl; formula (1-11-3): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is8Is n-hexyl.
The invention also provides a preparation method of the poly-fused ring conjugated macromolecule, which comprises the following steps:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a') to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein the content of the first and second substances,
formula (2)
Formula (a')
In the method, the group
R1-R6As described above, the present invention is not described in detail herein.
Wherein, the compound shown in the formula (2) is described above, and the invention is not repeated herein.
The compound represented by the formula (a ') may be appropriately selected according to the group a ', and for example, specific examples of the compound represented by the formula (a ') may include: formula (a' -1)
According to the present invention, the aldehyde group connected to both ends of the compound represented by formula (2) can be subjected to dehydration condensation with the compound represented by formula (a ') to form the compound represented by formula (1), wherein the amount of the compound represented by formula (2) and the compound represented by formula (a ') used is not particularly limited as long as the compound represented by formula (1) can be obtained, and preferably, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a ') is 1: 2-100, more preferably 1: 4-10.
According to the present invention, the reaction is carried out in the presence of a basic compound, so that a basic environment can be provided to the reaction system, and the kind and amount of the basic compound can be selected as described hereinabove.
According to the present invention, the kind and amount of the organic solvent may be selected as described hereinabove.
According to the present invention, preferably, the dehydration condensation reaction conditions include: the temperature is 20-100 deg.C (such as 50-100 deg.C), and the time is 10min-48h (such as 10-20 h). More preferably, the conditions of the dehydration condensation reaction include: the temperature is 60-80 ℃ and the time is 10-15 h.
In order to ensure the smooth proceeding of the reaction, the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after all the raw materials are added, the non-reactive gas may be introduced into the reaction system for 20-40min to remove air. The inert gas may be, for example, argon, helium, nitrogen, or the like.
According to the present invention, in order to extract the compound represented by the formula (1) from the reaction solution, the method further comprises a post-treatment step, for example, mixing the dehydration condensation reaction product with methanol (the amount of methanol may be, for example, 200-1000mL relative to the total volume of 100mL of the reaction solution), then carrying out solid-liquid separation, and carrying out chromatographic separation on the obtained solid phase by using a silica gel chromatographic column (200-300 mesh silica gel may be used, and the eluent may be a mixed solution of petroleum ether and dichloromethane in a volume ratio of 1: 0.2-3).
The invention also provides a photovoltaic material containing one or more of the poly-fused ring conjugated macromolecules.
According to the present invention, the photovoltaic material is not particularly limited as long as it contains the above-mentioned multiple-fused ring conjugated macromolecule of the present invention, and the photovoltaic material preferably refers to an electron donor material and/or an electron acceptor material in a light trapping active layer in a solar cell.
For example, the electron donor polymer material PBnDT-FTAZ may be mixed with the conjugated macromolecule provided by the present invention in a weight ratio of 0.5 to 4: 1 as a photovoltaic material, in particular as a photovoltaic material for a light-trapping active layer of a solar cell, wherein the conjugated macromolecules provided by the invention act as electron acceptor materials.
The structural units of the polymer material PBnDT-FTAZ are respectively as follows:
The invention also provides a solar cell which comprises a light-trapping active layer, wherein the electron donor material and/or the electron acceptor material in the light-trapping active layer contain one or more of the poly-fused ring conjugated macromolecules.
According to the present invention, the structure of the solar cell is not particularly limited as long as the electron donor material and/or the electron acceptor material in the active layer for light trapping thereof contains the above-mentioned conjugated macromolecule, so that the photoelectric conversion efficiency of the solar cell can be effectively improved.
In particular, the conjugated macromolecules of the invention are suitable for use in organic solar cells, in particular as electron acceptor materials in combination with other electron donor materials to form a light-trapping active layer of a solar cell. As such an electron donor material there may be mentioned, for example, the polymeric material PBnDT-FTAZ, as defined above.
Wherein, the polymer material PBnDT-FTAZ can be mixed with the conjugated macromolecule provided by the invention in a weight ratio of 0.5-4: 1 are combined to form the active layer for light trapping.
The invention also provides a preparation method of the solar cell, wherein the method comprises the step of using an electron donor material and/or an electron acceptor material containing one or more of the multi-fused ring conjugated macromolecules to form a light-trapping active layer.
According to the present invention, the process for preparing the solar cell is not particularly limited, and may be performed by a method conventional in the art, for example, the process may include:
coating a ZnO layer as a cathode modification layer (with the thickness of 20-50nm for example) on conductive glass (such as indium tin oxide glass and ITO) as a cathode, drying, coating a mixture of a polymer material PBnDT-FTAZ and the conjugated macromolecules provided by the invention as an active layer on the ZnO layer, drying, and performing vacuum evaporation on molybdenum oxide (with the thickness of 5-10nm for example) and Ag (with the thickness of 50-100nm for example) as an anode.
The conjugated macromolecule provided by the invention has a stronger visible light absorption peak, for example, a strong absorption peak in the wavelength range of 600-850 nm; the conjugated macromolecule has good thermal stability, can resist the temperature of about 310 ℃ without decomposition; the cyclic voltammetry test result shows that the HOMO energy level and the LUMO energy level of the material can be matched with the energy levels of most common electron donor materials, and the material has better capability of accepting electrons or holes, and is very favorable for being used as a photovoltaic material of a solar cell, in particular to an electron acceptor and/or an electron donor material, especially as an electron acceptor material.
The solar cell provided by the invention has high short-circuit current, such as 15mA cm-2Above, preferably up to 20mA cm-2(ii) a A high open circuit voltage, for example, 0.8V or more, preferably 0.9V or more; higher filling factor, for example, up to 65% or more, preferably up to 70% or more; a high photoelectric conversion rate (PCE) may be, for example, 8.9% or more, preferably 12%.
The present invention will be described in detail below by way of examples.
In the following examples:1h NMR was measured using a nuclear magnetic resonance apparatus model AVANCE 400 from Bruker. MS (MALDI) was measured using a Bruker Daltonics Biflex III MALDI-TOF Analyzer model mass spectrometer. The UV-visible absorption spectrum was measured using a Jasco V-570spectrophotometer model UV-visible spectrophotometer. The cyclic voltammogram was measured using a cyclic voltammeter model CHI660C electrochemical work. The I-V curve is measured by B2912A Precision Source/measurement Unit (Agilent Technologies), from which parameters such as short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency can be obtained. The polymer donor material PBnDT-FTAZ was prepared by the method in document j.am.chem.soc.2011,133, 4625.
Preparation example 1
This preparation example is illustrative of the method for producing the compound represented by the formula (2-7-2).
As shown in the above reaction scheme, a compound represented by the formula IT (102mg, 0.1 mmol; available from South technologies, Inc., Nakay, Suzhou), tetrahydrofuran (20mL) was addedArgon was introduced into the reaction vessel and stirred at-78 ℃ for 1 h. N-butyllithium (0.19mL, 0.3mmol,1.6M) was slowly added dropwise, stirred at-78 deg.C for 2h, N-dimethylformamide (36.6mg, 0.5mmol) was added, and the reaction product was slowly brought to room temperature (about 25 deg.C) and stirred overnight (about 12 h). Then, water (0.2mL) was added for quenching, extraction was performed with saturated brine and dichloromethane, drying was performed with magnesium sulfate, and spin-drying was performed to obtain a precipitate, which was chromatographed on a silica gel column (using 200-300 mesh silica gel, eluent petroleum ether/dichloromethane in a volume ratio of 2: 1) to obtain a bright yellow solid (91mg, yield 84.6%), which was the compound represented by the formula (2-7-2).1H NMR(400MHz,CDCl3):δ9.89(s,2H),7.94(s,2H),7.62(s,2H),7.16(d,J＝8.4Hz,8H),7.11(d,J＝8.4Hz,8H),2.58(t,J＝7.6Hz,8H),1.66(m,8H),1.31(m,24H),0.89(m,12H).MS(MALDI):m/z 1077(M+1).
Preparation example 2
This preparation example is illustrative of the method for producing the compound represented by the formula (2-7-3).
As shown in the above reaction formula, a compound represented by the formula IT-Th (104mg, 0.1 mmol; available from Solomon organic photoelectric technology, Beijing, Ltd.) and tetrahydrofuran (20mL) were added to a reaction vessel, and stirred at-78 ℃ for 1 hour under argon gas. N-butyllithium (0.2mL, 0.32mmol,1.6M) was slowly added dropwise, stirred at-78 deg.C for 2h, N-dimethylformamide (32.9mg, 0.45mmol) was added, and the reaction product was slowly brought to room temperature (about 25 deg.C) and stirred overnight (about 12 h). Then, water (0.2mL) was added for quenching, extraction was performed with saturated brine and dichloromethane, drying was performed with magnesium sulfate, and spin-drying was performed to obtain a precipitate, which was chromatographed on a silica gel column (using 200-mesh 300-mesh silica gel, eluent petroleum ether/dichloromethane in a volume ratio of 1.5: 1) to obtain a bright yellow solid (65mg, yield 59.1%), which was the compound represented by the formula (2-7-3).1H NMR(400MHz,CDCl3):δ9.94(s,2H),7.97(s,2H),7.79(s,2H),6.81(d,J＝3.2Hz,4H),6.57(d,J＝3.6Hz,4H),2.71(t,J＝7.6Hz,8H),1.61(m,8H),1.33(m,24H),0.87(m,12H).MS(MALDI):m/z 1099(M+).
Preparation example 3
This preparation example is illustrative of the method for producing the compound represented by the formula (2-9-2).
As shown in the above reaction scheme, a compound represented by formula IBT (226mg, 0.2 mmol; available from Soviet Nakay technologies, Ltd.) and tetrahydrofuran (35mL) were charged into a reaction vessel, and stirred at-78 ℃ for 1 hour under argon. N-butyllithium (0.4mL, 0.64mmol,1.6M) was slowly added dropwise, stirred at-78 deg.C for 1.5h, N-dimethylformamide (65.8mg, 0.9mmol) was added, and the reaction product was slowly brought to room temperature (about 25 deg.C) and stirred overnight (about 12 h). Then adding water (0.4mL) for quenching, extracting by using saturated brine and dichloromethane, drying by magnesium sulfate, spin-drying, and carrying out chromatographic separation on the obtained precipitate by using a silica gel chromatographic column (200-300-mesh silica gel is adopted, and the eluent is petroleum ether/dichloromethane with the volume ratio of 1: 1) to obtain an orange-red solid (159mg, the yield is 67 percent), namely the compound shown as the formula (2-9-2).1H NMR(400MHz,CDCl3):δ9.88(s,2H),7.88(s,2H),7.62(s,2H),7.18(d,J＝8.1Hz,8H),7.10(d,J＝8.1Hz,8H),2.54(t,J＝7.8Hz,8H),1.55(m,8H),1.27(m,24H),0.83(t,J＝6.6Hz,12H).MS(MALDI):m/z 1187(M+).
Preparation example 4
This preparation example is illustrative of the method for producing the compound represented by the formula (2-11-2).
As shown in the above reaction scheme, a compound represented by the formula ITT (186.4mg, 0.15 mmol; available from Scotch technologies, Suzhou), tetrahydrofuran (30mL) was charged into a reaction vessel, and stirred at-78 ℃ for 1h under argon. N-butyllithium (0.38mL, 0.6mmol,1.6M) was slowly added dropwise, stirred at-78 deg.C for 1.5h, N-dimethylformamide (51.2mg, 0.7mmol) was added, the reaction product was slowly brought to room temperature (about 25 deg.C), stirred overnight(about 12 h). Then, water (0.4mL) was added for quenching, extraction was performed with saturated brine and dichloromethane, drying was performed with magnesium sulfate, spin-drying was performed, and the obtained precipitate was chromatographed on a silica gel column (using 200-mesh 300-mesh silica gel, eluent petroleum ether/dichloromethane in a volume ratio of 1: 1) to obtain a red solid (106mg, yield 54.4%), which was the compound represented by the formula (2-11-2).1H NMR(400MHz,CDCl3):δ9.81(s,2H),7.86(s,2H),7.60(s,2H),7.19(d,J＝8.1Hz,8H),7.04(d,J＝8.1Hz,8H),2.46(t,J＝7.8Hz,8H),1.52(m,8H),1.24(m,24H),0.82(t,J＝6.6Hz,12H).MS(MALDI):m/z 1298(M+).
Preparation example 5
This preparation example is intended to illustrate the preparation of the compounds represented by the formulae (a-2) and (a-3).
As shown in the above reaction scheme, 5-fluoro-1, 3-indandione (820mg, 5 mmol; from Ark Co.), malononitrile (660mg, 10mmol), and ethanol (30mL) were charged into a reaction vessel, and stirred at 25 ℃ for 30 minutes under argon. Sodium acetate (492mg, 6mmol) was added slowly and stirred at 25 ℃ for 2h, water (40mL) was added and stirred for 1.5 h. Then, concentrated hydrochloric acid was added to adjust the pH to 2, and the mixture was filtered through a filter paper, washed with water (300mL), and the obtained precipitate was chromatographed on a silica gel column (using 200-mesh 300-mesh silica gel, and the eluent was methanol/chloroform at a volume ratio of 1: 5) to obtain an off-white solid (610mg, yield 57.5%) which was a mixture of the compound represented by the formula (a-2) (71 mol%) and the compound represented by the formula (a-3) (29 mol%). Of mixtures1H NMR(400MHz,CDCl3):δ8.68(dd,J＝8.8Hz,0.28H),7.61(dd,J＝8.2Hz,0.72H),8.01(m,0.76H),7.61(m,0.36H),7.55(m,1H),3.76(d,2H).MS(EI):m/z 212(M+).
Preparation example 6
This preparation example is illustrative of the method for producing the compound represented by the formula (a-1).
As shown in the above reaction scheme, 4-fluoro-1, 3-indandione (410mg, 2.5 mmol; available from Ark Co.), malononitrile (330mg, 5mmol), and ethanol (20mL) were charged into a reaction vessel, and stirred at 25 ℃ for 30 minutes under argon. Sodium acetate (246mg, 3mmol) was added slowly and stirred at 25 ℃ for 2h, water (30mL) was added and stirred for 1.5 h. Then, concentrated hydrochloric acid was added to adjust the pH to 2, the mixture was filtered through filter paper and washed with water (300mL), and the obtained precipitate was chromatographed on a silica gel column (200-mesh 300-mesh silica gel was used and the eluent was methanol/chloroform at a volume ratio of 1: 2) to obtain a brown solid (190mg, yield 35.8%), which was the compound represented by the formula (a-1).1H NMR(400MHz,CDCl3):δ8.48(d,J＝8.1Hz,1H),7.89(m,1H),7.49(t,J＝8.4Hz,1H),3.76(s,2H).MS(EI):m/z 212(M+).
Preparation example 7
This preparation example is illustrative of the method for producing the compound represented by the formula (a-5).
As shown in the above reaction scheme, 5, 6-difluoro-1, 3-indandione (201mg, 1.1 mmol; synthesized according to the method in Planells, M.; Robertson, N.Eur.J.Org.chem.2012,2012, 4947), malononitrile (145mg, 2.2mmol), ethanol (20mL) were added to the reaction vessel, and the mixture was stirred at 25 ℃ for 30 minutes under argon. Sodium acetate (107mg, 1.3mmol) was added slowly and stirred at 25 ℃ for 2h, water (30mL) was added and stirred for 1.5 h. Then, concentrated hydrochloric acid was added to adjust the pH to 2, the mixture was filtered through a filter paper and washed with water (400mL), and the obtained precipitate was chromatographed on a silica gel column (200-mesh 300-mesh silica gel was used and the eluent was methanol/chloroform at a volume ratio of 1: 1) to obtain a brown solid (115mg, yield 44.6%), which was the compound represented by the formula (a-5).1H NMR(400MHz,CDCl3):δ8.46(dd,J＝6.4Hz,1H),7.76(t,J＝7.6Hz,1H),3.76(s,2H).MS(EI):m/z 230(M+).
Example 1
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-5-2) (96.3mg, 0.1 mmol; available from Soochet technologies, Inc., Nakai, Suzhou), a mixture (84.8mg, 0.4mmol) of the compound represented by the formula (a-2) and the compound represented by the formula (a-3) obtained in the above preparation example 5, pyridine (0.6mL, 0.72mmol) and chloroform (35mL) were charged into a reaction vessel, purged with argon for 20min, and then refluxed at 65 ℃ for 15 h. After cooling to room temperature (about 25 ℃ C.), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel with petroleum ether/dichloromethane as an eluent in a volume ratio of 1: 1) to give a deep blue solid (87mg, yield 64%) which is a mixture of the multiple-and fused-ring conjugated macromolecules represented by the formula (1F-5-F1) which is a compound represented by the formula (1F-5-5), the formula (1F-5-8) and the formula (1F-5-35). Of mixtures1HNMR(400MHz,CDCl3):δ8.89(d,2H),8.71(dd,J＝4.8Hz,0.6H),8.38(dd,J＝8.8Hz,1.4H),7.91(dd,J＝5.2Hz,1.4H),7.73(t,J＝4.4Hz,4H),7.54(dd,J＝2.8Hz,0.6H),7.42(m,2H),7.13(d,J＝8.4Hz,16H),2.58(t,J＝7.6Hz,8H),1.61(m,8H),1.30(m,24H),0.88(m,12H).MS(MALDI):m/z 1351.8(M+1).
The UV-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-5-F1) is shown in FIG. 1, wherein the mixture has a strong absorption peak in the wavelength range of 600-750nm and the maximum molar extinction coefficient of 2.42 × 105M–1·cm–1The film absorbs most strongly at 704 nm.
The cyclic voltammogram is shown in FIG. 2, the HOMO energy level is-5.84 eV, the LUMO energy level is-3.93 eV, and the band gap is 1.91eV, which shows that the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1F-5-F1) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 2
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-5-1) (66mg, 0.1 mmol; available from Solidago organic photoelectric technology (Beijing) Co., Ltd.), a mixture (84.8mg, 0.4mmol) of the compounds represented by the formulae (a-2) and (a-3) obtained in the above preparation example 5, pyridine (0.65mL, 0.78mmol) and chloroform (30mL) were charged into a reaction vessel, purged with argon for 15min, followed by refluxing at 65 ℃ for 13 h. After cooling to room temperature (about 25 ℃ C.), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel with an eluent of petroleum ether/dichloromethane in a volume ratio of 1: 1.5) to give a brown solid (67mg, yield 64%) which was a mixture of the multiple-and-fused ring conjugated macromolecules represented by the formula (1F-5-F2) which was the compounds represented by the formula (1F-5-4), the formula (1F-5-7) and the formula (1F-5-34). Of mixtures1H NMR(400MHz,CDCl3):δ8.98(d,2H),8.74(dd,J＝4.4Hz,0.6H),8.40(d,J＝8.8Hz,1.4H),7.95(dd,J＝6.4Hz,1.4H),7.73(d,2H),7.61(s,2H),7.58(m,0.6H),7.44(t,J＝6.4Hz,2H),2.07(m,4H),1.95(m,4H),1.14(m,24H),0.78(m,20H).MS(MALDI):m/z 1047(M+1).
The UV-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-5-F2) is shown in FIG. 3, wherein the mixture has a strong absorption peak in the wavelength range of 600-800nm and the maximum molar extinction coefficient of 2.12X 105M–1·cm–1The film absorbs most strongly at around 730 nm.
The cyclic voltammogram is shown in FIG. 4, the HOMO level is-5.72 eV, the LUMO level is-3.99 eV, and the band gap is 1.73eV, which shows that the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1F-5-F2) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 3
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-5-1) (100mg, 0.15 mmol; available from Solomon organic photoelectric technology (Beijing) Co., Ltd.), a compound represented by the formula (a-5) (138mg, 0.6mmol), pyridine (0.7mL, 0.84mmol) and chloroform (35mL) were charged into a reaction vessel, and the reaction was refluxed at 65 ℃ for 14 hours under argon gas for 15 minutes. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel chromatography column (200-300 mesh silica gel was used, and the eluent was petroleum ether/dichloromethane at a volume ratio of 3: 1) to obtain a dark brown solid (93mg, yield 57%) which was the poly-fused ring conjugated macromolecule represented by the formula (1F-5-13).1H NMR(400MHz,CDCl3):δ8.98(s,2H),8.57(dd,J＝6.4Hz,2H),7.72(m,4H),7.62(s,2H),2.08(m,4H),1.95(m,4H),1.14(m,24H),0.8(m,20H).MS(MALDI):m/z 1084(M+1).
The UV-visible absorption spectrum of the conjugated macromolecule with multiple condensed rings shown in the formula (1F-5-13) is shown in FIG. 5, wherein the UV-visible absorption spectrum has a strong absorption peak in the wavelength range of 600-750nm, and the maximum molar extinction coefficient is 2.4 × 105M–1·cm–1The film absorbs most strongly at around 724 nm.
The cyclic voltammogram is shown in FIG. 6, the HOMO energy level is-5.73 eV, the LUMO energy level is-4.06 eV, and the band gap is 1.67eV, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1F-5-13) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 4
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a mixture of the compound represented by the formula (2-7-2) (110mg, 0.1mmol), the compound represented by the formula (a-2) and the compound represented by the formula (a-3) obtained in the above production example 5The mixture (84.8mg, 0.4mmol), pyridine (0.7mL, 0.84mmol) and chloroform (35mL) were added to the reaction vessel, purged with argon for 15min, and then refluxed at 65 ℃ for 16 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel with an eluent of petroleum ether/dichloromethane at a volume ratio of 1: 1) to give a bluish black solid (110mg, yield 75%) as a mixture of the multiple-and-fused ring-conjugated macromolecules represented by formula (1F-7-F1), which is a compound represented by formula (1F-7-5), formula (1F-7-8) and formula (1F-7-35). Of mixtures1H NMR(400MHz,CDCl3):δ8.60(s,2H),8.71(dd,J＝4.0Hz,0.5H),8.36(dd,J＝1.6Hz,1.5H),8.23(d,J＝7.6Hz,2H),7.92(dd,J＝5.2Hz,1.5H),7.64(s,2H),7.55(dd,J＝2.8Hz,0.5H),7.41(m,2H),7.21(d,J＝8.4Hz,8H),7.14(d,J＝8.4Hz,8H),2.57(t,J＝8Hz,8H),1.61(m,8H),1.29(m,24H),0.86(t,J＝6.4Hz,12H).MS(MALDI):m/z 1463.7(M+1).
The UV-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-7-F1) is shown in FIG. 7, wherein the mixture has a strong absorption peak in the wavelength range of 600-800nm and the maximum molar extinction coefficient of 2.2X 105M–1·cm–1The film has the strongest absorption at the position of about 734 nm; the maximum absorption peak of the film is 48nm red-shifted from the solution.
The cyclic voltammogram is shown in FIG. 8, the HOMO level is-5.63 eV, the LUMO level is-3.98 eV, and the band gap is 1.65eV, which shows that the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1F-7-F1) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 5
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-7-3) (110mg, 0.1mmol), the formula (a-2) obtained in the above production example 5 anda mixture (84.8mg, 0.4mmol) of the compound represented by the formula (a-3), pyridine (0.7mL, 0.84mmol) and chloroform (30mL) were added to a reaction vessel, and argon was introduced for 25min, followed by reflux at 65 ℃ for 15 h. After cooling to room temperature (about 25 ℃ C.), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel with petroleum ether/dichloromethane as an eluent in a volume ratio of 1: 1) to give a turquoise solid (75mg, yield 50.4%) which was a mixture of the multiple-and-fused ring conjugated macromolecules represented by the formula (1F-7-F3) which was the compounds represented by the formula (1F-7-6), the formula (1F-7-9) and the formula (1F-7-36). Of mixtures1H NMR(400MHz,CDCl3):δ8.90(s,2H),8.72(dd,J＝4.4Hz,0.4H),8.39(d,1.6H),8.27(d,2H),7.94(dd,J＝5.2Hz,1.6H),7.82(s,2H),7.58(dd,J＝2.4Hz,0.4H),7.42(m,2H),6.88(m,4H),6.61(m,4H),2.72(t,J＝2.4Hz,8H),1.64(m,8H),1.27(m,24H),0.83(m,12H).MS(MALDI):m/z 1488(M+1).
The UV-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-7-F3) is shown in FIG. 9, wherein the mixture has a strong absorption peak in the wavelength range of 600-800nm and the maximum molar extinction coefficient of 1.79X 105M–1·cm–1The film absorbs most strongly at around 728 nm.
The cyclic voltammogram is shown in FIG. 10, the HOMO level is-5.74 eV, the LUMO level is-4.01 eV, and the band gap is 1.73eV, which shows that the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1F-7-F3) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 6
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-7-3) (165mg, 0.15mmol), a compound represented by the formula (a-5) (127mg, 0.6mmol), pyridine (0.9mL, 1.08mmol) and chloroform (40mL) were added to a reaction vesselArgon was introduced into the vessel for 30min, followed by reflux at 65 ℃ for 16 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel chromatography column (200-300 mesh silica gel was used, and the eluent was petroleum ether/dichloromethane at a volume ratio of 3: 1) to obtain a dark green solid (100mg, yield 44%), which was the poly-fused ring conjugated macromolecule represented by the formula (1F-7-15).1H NMR(400MHz,CDCl3):δ8.89(s,2H),8.55(t,J＝8.8Hz,2H),8.27(s,2H),7.83(d,2H),7.70(t,J＝7.6Hz,2H),6.88(m,4H),6.61(m,4H),2.72(t,J＝8.0Hz,8H),1.62(m,8H),1.31(m,24H),0.82(m,12H).MS(MALDI):m/z 1523(M+1).
The UV-visible absorption spectrum of the conjugated macromolecule with multiple condensed rings shown in the formula (1F-7-15) is shown in FIG. 11, wherein the UV-visible absorption spectrum has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.23 × 105M–1·cm–1The film has the strongest absorption at about 736 nm.
The cyclic voltammogram is shown in FIG. 12, the HOMO energy level is-5.75 eV, the LUMO energy level is-4.07 eV, and the band gap is 1.68eV, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1F-7-15) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 7
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-9-2) (154mg, 0.13mmol), a mixture (106mg, 0.5mmol) of the compounds represented by the formulae (a-2) and (a-3) obtained in the above production example 5, pyridine (0.9mL, 1.08mmol) and chloroform (30mL) were charged into a reaction vessel, passed through argon for 30min, and then refluxed at 65 ℃ for 14 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the resulting precipitate was chromatographed on a silica gel column (200-300 mesh silica gel was used, eluent was petroleum ether/dichloromethane in a volume ratio of 1: 1)And separating to obtain a turquoise solid (100mg, the yield is 48.8 percent), namely the poly-fused ring conjugated macromolecule shown as the formula (1F-9-F1), which is a mixture of the compounds shown as the formula (1F-9-5), the formula (1F-9-8) and the formula (1F-9-35). Of mixtures1H NMR(400MHz,CDCl3):δ8.91(d,2H),8.67(dd,J＝4.4Hz,0.5H),8.35(d,1.5H),7.96(d,J＝10.8Hz,2H),7.90(dd,J＝5.2Hz,1.5H),7.64(s,2H),7.53(m,0.5H),7.37(m,2H),7.21(d,J＝8.4Hz,8H),7.14(d,J＝8Hz,8H),2.59(t,J＝8Hz,8H),1.61(m,8H),1.30(m,24H),0.87(m,12H).MS(MALDI):m/z1475.9(M+1).
The UV-visible absorption spectrum of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-9-F1) is shown in FIG. 13, wherein the mixture has a strong absorption peak in the wavelength range of 600-800nm and the maximum molar extinction coefficient of 2.11X 105M–1·cm–1The film absorbs most strongly at around 728 nm.
The cyclic voltammogram is shown in FIG. 14, the HOMO level is-5.44 eV, the LUMO level is-3.98 eV, and the band gap is 1.46eV, which shows that the mixture of the three poly-fused ring conjugated macromolecules shown in the formula (1F-9-F1) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 8
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-9-2) (120mg, 0.1mmol), a compound represented by the formula (a-1) (84mg, 0.4mmol), pyridine (0.8mL, 0.96mmol) and chloroform (35mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 14 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by means of a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether/dichloromethane in a volume ratio of 1: 2) to obtain a turquoise solid (75mg, yield 47.5%) which was the multiple fused ring-sharing solid represented by the formula (1F-9-2)The yoke is a macromolecule.1H NMR(400MHz,CDCl3):δ8.94(s,2H),8.48(d,J＝8Hz,2H),7.96(s,2H),7.69(m,2H),7.64(s,2H),7.33(t,J＝8.4Hz,2H),7.2(d,J＝8.4Hz,8H),7.14(d,J＝8.4Hz,8H),2.58(t,J＝7.6Hz,8H),1.61(m,8H),1.29(m,24H),0.86(t,J＝6.4Hz,12H).MS(MALDI):m/z 1576.1(M+1).
The UV-visible absorption spectrum of the conjugated macromolecule with multiple condensed rings shown in the formula (1F-9-2) is shown in FIG. 15, wherein the UV-visible absorption spectrum has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.22 × 105M–1·cm–1The film absorbs most strongly at around 720 nm.
The cyclic voltammogram is shown in FIG. 16, the HOMO energy level is-5.46 eV, the LUMO energy level is-3.98 eV, and the band gap is 1.48eV, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1F-9-2) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 9
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-9-2) (154mg, 0.13mmol), a compound represented by the formula (a-5) (116mg, 0.55mmol), pyridine (0.9mL, 1.08mmol) and chloroform (35mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 15 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel chromatography column (200-300 mesh silica gel was used, and the eluent was petroleum ether/dichloromethane at a volume ratio of 2: 1) to obtain a black-green solid (95mg, yield 45.5%) which was the poly-fused ring conjugated macromolecule represented by the formula (1F-9-14).1H NMR(400MHz,CDCl3):δ8.91(s,2H),8.53(dd,J＝3.6Hz,2H),7.98(s,2H),7.67(m,4H),7.20(d,8H),7.14(d,8H),2.58(t,J＝8.0Hz,8H),1.62(m,8H),1.27(m,24H),0.87(m,12H).MS(MALDI):m/z 1612(M+1).
The formula (1F-9-14)The UV-visible absorption spectrum of the polycyclic conjugated macromolecule is shown in FIG. 17, wherein the UV-visible absorption spectrum has a strong absorption peak in the wavelength range of 600-800nm and the maximum molar extinction coefficient is 2.51 × 105M–1·cm–1The film absorbs most strongly at around 744 nm.
The cyclic voltammogram is shown in FIG. 18, the HOMO energy level is-5.49 eV, the LUMO energy level is-4.02 eV, and the band gap is 1.47eV, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1F-9-14) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 10
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-9-2) (120mg, 0.1mmol), a compound represented by the formula (a' -1) (78mg, 0.4 mmol; available from TCI Co., Ltd.), pyridine (0.8mL, 0.96mmol) and chloroform (30mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 15 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel column (200-300 mesh silica gel was used, and the eluent was petroleum ether/dichloromethane at a volume ratio of 1: 2) to obtain a turquoise solid (115mg, yield 74.6%), which was the poly-fused ring conjugated macromolecule represented by the formula (1-9-2).1H NMR(400MHz,CDCl3):δ8.92(d,J＝3.6Hz,2H),8.67(m,2H),7.91(dd,J＝6.8Hz,4H),7.69(m,4H),7.64(s,2H),7.21(d,J＝8Hz,8H),7.15(d,J＝8Hz,8H),2.58(t,J＝8Hz,8H),1.62(m,8H),1.30(m,24H),0.86(t,J＝6.4Hz,12H).MS(MALDI):m/z1539.4(M+1).
The UV-visible absorption spectrum of the conjugated macromolecule with multiple fused rings shown in the formula (1-9-2) is shown in FIG. 19, wherein the UV-visible absorption spectrum has a strong absorption peak in the wavelength range of 600-800nm, and the maximum molar extinction coefficient is 2.09X 105M–1·cm–1The film absorbs most strongly at about 706 nm; film(s)The maximum absorption peak of (a) is shifted 14nm more than the red in solution.
The cyclic voltammogram is shown in FIG. 20, the HOMO energy level is-5.41 eV, the LUMO energy level is-3.90 eV, and the band gap is 1.51eV, which shows that the poly-fused ring conjugated macromolecule shown in the formula (1-9-2) has better electron accepting capability and can be matched with the energy level of most common electron donor materials.
Example 11
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-11-2) (130mg, 0.1mmol), a mixture (84mg, 0.4mmol) of the compounds represented by the formulae (a-2) and (a-3) obtained in preparation example 5 above, pyridine (0.7mL, 0.84mmol) and chloroform (40mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 13 h. After cooling to room temperature (about 25 ℃ C.), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by means of a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether/chloroform in a volume ratio of 1: 2) to obtain a dark green solid (83mg, yield 49%) which was a mixture of the multiple-and-fused ring conjugated macromolecules represented by the formula (1F-11-F1) which was the compounds represented by the formula (1F-11-5), the formula (1F-11-8) and the formula (1F-11-35). Of mixtures1H NMR(400MHz,CDCl3):δ8.93(d,J＝6.4Hz,2H),8.72(dd,J＝4.4Hz,0.5H),8.41(d,J＝8.8Hz,1.5H),8.03(d,J＝10.8Hz,2H),7.94(dd,J＝5.2Hz,1.5H),7.71(s,2H),7.59(m,0.5H),7.42(m,2H),7.24(d,J＝8.4Hz,8H),7.17(d,J＝8Hz,8H),2.63(t,J＝8Hz,8H),1.67(m,8H),1.33(m,24H),0.89(m,12H).MS(MALDI):m/z 1689(M+1).
Example 12
This example serves to illustrate the conjugated macromolecules of the invention and their preparation.
As shown in the above reaction scheme, a compound represented by the formula (2-11-2) (130mg, 0.1mmol), a compound represented by the formula (a' -1) (78mg, 0.4 mmol; available from TCI Co., Ltd.), pyridine (0.8mL, 0.96mmol) and chloroform (30mL) were charged into a reaction vessel, purged with argon for 25min, and then refluxed at 65 ℃ for 14 h. After cooling to room temperature (about 25 ℃), the reaction product was poured into 200mL of methanol and filtered, and the obtained precipitate was chromatographically separated by using a silica gel column (200-300 mesh silica gel was used, and the eluent was petroleum ether/dichloromethane at a volume ratio of 1: 2) to obtain a turquoise solid (78mg, yield 47%), which was the poly-fused ring conjugated macromolecule represented by the formula (1-11-2).1H NMR(400MHz,CDCl3):δ8.94(s,2H),8.81(m,2H),8.33(dd,J＝6.8Hz,4H),7.96(m,4H),7.76(s,2H),7.23(d,J＝8Hz,8H),7.18(d,J＝8Hz,8H),2.60(t,J＝8Hz,8H),1.63(m,8H),1.32(m,24H),0.88(t,J＝6.4Hz,12H).MS(MALDI):m/z1653(M+1).
Example 13
This example serves to illustrate the solar cell of the present invention.
Indium Tin Oxide (ITO) glass (purchased from Shenzhen glass float glass Co., Ltd.) as a cathode is cleaned by a detergent, then sequentially cleaned by deionized water, acetone and isopropanol in an ultrasonic mode, a ZnO cathode modification layer with the thickness of 30nm is coated in a spin mode after drying, and the ZnO cathode modification layer is dried for 30 minutes at the temperature of 200 ℃ for later use.
1.5mg of the mixture of the three poly-fused ring conjugated macromolecules represented by the formula (1F-5-F1) and 1mg of the polymer donor material PBnDT-FTAZ were mixed in 0.1mL of chloroform to obtain a mixed solution, which was spin-coated on the ZnO layer, and dried to obtain a light trapping active layer (having an effective area of 4 mm)2). Vacuum (absolute pressure 2X 10) on the active layer- 5Pa) vapor deposition thickness of about 5nm of MoO3(available from carbofuran technologies, inc.) and about 80nm of metallic Ag as the anode of the solar cell.
A solar light source was simulated with an AM1.5 filter (model XES-70S1, SAN-EI ELECTRIC Co., Ltd.) at 100mW/cm2The devices were tested for photovoltaic performance at light intensity calibrated by standard single crystal silicon solar cells (available from VLSI Standards Inc). The obtained I-V kojiThe lines were measured using B2912A Precision Source/measurement Unit (Agilent Technologies) and controlled by computer via Labview software.
The resulting I-V curve is shown in FIG. 21. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 21oc0.72V, short-circuit current JscIs 12.7mA cm-2The fill factor FF is 62% and the photoelectric conversion efficiency PCE is 5.7%.
Example 14
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F2) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 22. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 22oc0.74V, short-circuit current JscIs 15.5mA cm-2The fill factor FF is 66.7%, and the photoelectric conversion efficiency PCE is 7.63%.
Example 15
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1F-5-13) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 23. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 23oc0.65V, short-circuit current JscIs 14.7mA · cm-2The fill factor FF is 62.3%, and the photoelectric conversion efficiency PCE is 5.93%.
Example 16
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-7-F1) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 24. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 24oc0.79V, short-circuit current JscIs 15.3mA cm-2The fill factor FF was 61.5% and the photoelectric conversion efficiency PCE was 7.47%.
Example 17
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-7-F3) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 25. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 25oc0.84V, short-circuit current JscIs 19.7mA · cm-2The fill factor FF is 74% and the photoelectric conversion efficiency PCE is 12.1%.
Example 18
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1F-7-15) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 26. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 26oc0.75V, short-circuit current JscIs 17.2mA · cm-2The fill factor FF is 70% and the photoelectric conversion efficiency PCE is 9.2%.
Example 19
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-9-F1) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 27. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 27oc0.90V, short-circuit current JscIs 17.7mA · cm-2The fill factor FF is 67.8%, and the photoelectric conversion efficiency PCE is 10.8%.
Example 20
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1F-9-2) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 28. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 28oc0.93V, short-circuit current JscIs 16.7mA cm-2The fill factor FF is 64.8%, and the photoelectric conversion efficiency PCE is 10.1%.
Example 21
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1F-9-14) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 29. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 29oc0.85V, short-circuit current JscIs 19.68mA · cm-2The fill factor FF is 68.5% and the photoelectric conversion efficiency PCE is 11.5%.
Example 22
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1-9-2) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 30. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 30oc0.97V, short-circuit current JscIs 13.4mA cm-2The fill factor FF is 59.5%, and the photoelectric conversion efficiency PCE is 7.69%.
Example 23
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-11-F1) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 31. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 31oc0.91V, short-circuit current JscIs 17.3mA · cm-2The fill factor FF is 71% and the photoelectric conversion efficiency PCE is 11.2%.
Example 24
This example serves to illustrate the solar cell of the present invention.
A solar cell was finally prepared and tested according to the procedure described in example 13, except that 1.5mg of the polyacene ring conjugated macromolecule represented by the formula (1-11-2) was used in place of the mixture of three polyacene ring conjugated macromolecules represented by the formula (1F-5-F1).
The resulting I-V curve is shown in FIG. 32. The open circuit voltage V of the solar cell can be obtained by the I-V curve shown in FIG. 32oc0.92V, short-circuit current JscIs 14.5mA cm-2The fill factor FF is 60% and the photoelectric conversion efficiency PCE is 8%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (27)
1. A multiple-fused ring conjugated macromolecule, wherein the conjugated macromolecule is a compound represented by the following formula (1F):
formula (1F)
Wherein each group
Each independently represents 2 to 10 thiophene conjugated fused ring structures;
each group A is independently selected from one of the groups shown in the following formulas:
wherein R is3-R6At least one of which is F, the others are each independently selected from H, alkyl, alkoxy and alkylthio;
wherein each R is1Each independently selected from the group consisting of
A group shown and formula
A group shown;
each R is2Each independently selected from the group consisting of
A group shown;
each Z is independently selected from C, N and Si;
each X and each Y is independently selected from O, S and Se;
m is an integer of 0 to 6;
p is an integer of 0 to 6;
n is an integer of 0 to 6;
each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C12 aryl.
2. The polya-fused ring conjugated macromolecule of claim 1, wherein each group is
Each independently represents 2 to 5 thiophene conjugated fused ring structures; r3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O and S; m is an integer of 0 to 4; p is an integer of 0 to 4; n is an integer of 0 to 4; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, and C6-C10 aryl.
3. The polya-fused ring conjugated macromolecule of claim 2, wherein each group is
Each independently represents 2 to 4 thiophene conjugated fused ring structures; r3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, and C1-C20 alkylthio; each Z is independently selected from C and N; each R is7Each R9And each R11Each independently selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 alkylthio; each R is8And each R10And each independently selected from the group consisting of H, C4-C10 alkyl, C4-C10 alkoxy, and C4-C10 alkylthio.
4. The polya-fused ring conjugated macromolecule of claim 3, wherein R3-R6At least one of which is F, the others are each independently selected from the group consisting of H, C1-C10 alkyl, C1-C10 alkoxy, and C1-C10 alkylthio; each Z is independently selected from C and N; m is 0, 1, 2 or 3; p is 0, 1, 2 or 3; n is 0, 1, 2 or 3; each R is7Each R9And each R11Each independently selected from H, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio, and n-butylthio; each R is8And each R10And each is independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
5. The poly-fused ring conjugated macromolecule of claim 1, wherein the conjugated macromolecule is one of the compounds represented in the following formula:
formula (1F-7):
formula (1F-9):
formula (1F-11):
6. the poly-fused ring conjugated macromolecule of claim 5, wherein the definition: the radical A-1 is
The group A-2 is
The radical A-3 is
The group A-4 is
The radical A-5 is
The radical A-6 is
The radical A-7 is
The radical A-8 is
The radical A-9 is
The radical A-10 is
The radical A-11 is
The conjugated macromolecule is one of the compounds shown in the following formula:
formula (1F-7-1): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl;
formula (1F-7-2): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-3): in the formula (1F-7), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-4): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl;
formula (1F-7-5): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-6): in the formula (1F-7), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-7): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-7-8): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-9): in the formula (1F-7), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-10): in the formula (1F-7), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl;
formula (1F-7-11): in the formula (1F-7), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-12): in the formula (1F-7), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-13): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are both n-hexyl;
formula (1F-7-14): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-15): in the formula (1F-7), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is8Is n-hexylA group;
formula (1F-7-16): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl;
formula (1F-7-17): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-18): in the formula (1F-7), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-19): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl;
formula (1F-7-20): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-21): in the formula (1F-7), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-22): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl;
formula (1F-7-23): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-24): in the formula (1F-7), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-25): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl;
formula (1F-7-26): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-27): in the formula (1F-7), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-28): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are both n-hexyl;
formula (1F-7-29): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-30): in the formula (1F-7), Z is C, A is A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-31): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl;
formula (1)F-7-32): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-33): in the formula (1F-7), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-7-34): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-7-35): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-7-36): in the formula (1F-7), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-1): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl;
formula (1F-9-2): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-3): in the formula (1F-9), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-4): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl;
formula (1F-9-5): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-6): in the formula (1F-9), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-7): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-9-8): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-9): in the formula (1F-9), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-10): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl;
formula (1F-9-11): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-12): in the formula (1F-9), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-13): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are both n-hexyl;
formula (1F-9-14): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-15): in the formula (1F-9), Z is C, A is A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-16): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl;
formula (1F-9-17): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-18): in the formula (1F-9), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-19): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl;
formula (1F-9-20): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-21): in the formula (1F-9), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-22): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl;
formula (1F-9-23): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-24): in the formula (1F-9), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-25): in the formula (1F-9), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl;
formula (1F-9-26): in the formula (1F-9), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-27)): in the formula (1F-9), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-28): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are both n-hexyl;
formula (1F-9-29): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-30): in the formula (1F-9), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-31): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl;
formula (1F-9-32): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-33): in the formula (1F-9), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-9-34): in the formula (1F-9), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-9-35): in the formula (1F-9), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-9-36): in the formula (1F-9), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-1): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are both n-hexyl;
formula (1F-11-2): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-3): in the formula (1F-11), Z is C, A is A-1, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-4): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are both n-hexyl;
formula (1F-11-5): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-6): in the formula (1F-11), Z is C, A is A-2, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-7): in the formula (1F-11), Z is C, A is A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-11-8): in the formula (1F-11), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-9): in the formula (1F-11), Z is C, A is A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-10): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are both n-hexyl;
formula (1F-11-11): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-12): in the formula (1F-11), Z is C, A is A-4, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-13): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are both n-hexyl;
formula (1F-11-14): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-15): in the formula (1F-11), Z is C, A is a group A-5, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-16): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are both n-hexyl;
formula (1F-11-17): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-18): in the formula (1F-11), Z is C, A is A-6, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-19): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are both n-hexyl;
formula (1F-11-20): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-21): in the formula (1F-11), Z is C, A is a group A-7, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-22): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are both n-hexyl;
formula (1F-11-23): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-24): in the formula (1F-11), Z is C, A is A-8, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-25): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are both n-hexyl;
formula (1F-11-26): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-27): in the formula (1F-11), Z is C, A is A-9, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-28): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are both n-hexyl;
formula (1F-11-29): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-30): in the formula (1F-11), Z is C, A is a group A-10, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-31): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are both n-hexyl;
formula (1F-11-32): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-33): in the formula (1F-11), Z is C, A is a group A-11, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1F-11-34): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are both n-hexyl;
formula (1F-11-35): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1F-11-36): in the formula (1F-11), Z is C, one A is a group A-2, the other A is a group A-3, R2Is absent, R1Are all made of
And R is8Is n-hexyl.
7. A method of preparing a polya-fused ring conjugated macromolecule of any of claims 1-6, comprising:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a) to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1F); wherein the content of the first and second substances,
formula (2)
Formula (a)
8. The method of claim 7, wherein the molar ratio of the compound of formula (2) to the compound of formula (a) is 1: 2-100.
9. The method of claim 7 or 8, wherein the conditions of the dehydration condensation reaction comprise: the temperature is 20-100 deg.C, and the time is 10min-48 h.
10. The method of claim 7, wherein the basic compound is one or more of piperidine, pyridine, and triethylamine.
11. The method according to claim 10, wherein the basic compound is used in an amount of 0.1 to 1000mmol relative to 1mmol of the compound represented by formula (2).
12. The method of claim 10, wherein the organic solvent is chloroform and/or dichloromethane.
13. A multiple-fused ring conjugated macromolecule, wherein the conjugated macromolecule is a compound represented by the following formula (1):
formula (1)
Wherein each group
Each independently represents 3 to 10 thiophene conjugated fused ring structures;
each group A' is independently selected from one of the groups represented by the following formulas:
wherein R is3-R6Each independently selected from H, alkyl, alkoxy, and alkylthio;
wherein each R is1Each independently selected from the group consisting of
A group shown and formula
A group shown;
each R is2Each independently selected from the group consisting of
A group shown;
each Z is independently selected from C, N and Si;
each X and each Y is independently selected from O, S and Se;
m is an integer of 0 to 6;
p is an integer of 0 to 6;
n is an integer of 0 to 6;
each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C12 aryl.
14. The method of claim 13A polycyclic and fused ring conjugated macromolecule in which each group
Each independently represents 3 to 5 thiophene conjugated fused ring structures; r3-R6Each independently selected from the group consisting of H, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio; each Z is independently selected from C, N and Si; each X and each Y is independently selected from O and S; m is an integer of 0 to 4; p is an integer of 0 to 4; n is an integer of 0 to 4; each R is7Each R8Each R9Each R10And each R11Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, and C6-C10 aryl.
15. The polya-fused ring conjugated macromolecule of claim 14, wherein each group is
Each independently represents 3 to 4 thiophene conjugated fused ring structures; r3-R6Each independently selected from the group consisting of H, C1-C20 alkyl, C1-C20 alkoxy, and C1-C20 alkylthio; each Z is independently selected from C and N; each R is7Each R9And each R11Each independently selected from the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 alkylthio; each R is8And each R10And each independently selected from the group consisting of H, C4-C10 alkyl, C4-C10 alkoxy, and C4-C10 alkylthio.
16. The polya-fused ring conjugated macromolecule of claim 15, wherein R3-R6Each independently selected from the group consisting of H, C1-C10 alkyl, C1-C10 alkoxy, and C1-C10 alkylthio; each Z is independently selected from C and N; m is 0, 1, 2 or 3; p is 0, 1, 2 or 3; n is 0, 1, 2 or 3; each R is7Each R9And each R11Each independently selected from H, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-propylButoxy, methylthio, ethylthio, n-propylthio and n-butylthio; each R is8And each R10And each is independently selected from the group consisting of H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octoxy, 2-ethylhexoxy, n-butylthio, n-pentoxy, n-hexoxy, n-octoxy, and 2-ethylhexoxy.
17. The polya-fused ring conjugated macromolecule of claim 13, wherein the conjugated macromolecule is one of the compounds represented in the following formula:
formula (1-9):
formula (1-11):
18. the polya-fused ring conjugated macromolecule of claim 17, wherein,
defining: the radical A' -1 is
The conjugated macromolecule is one of the compounds shown in the following formula:
formula (1-9-1): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are both n-hexyl;
formula (1-9-2): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1-9-3): in the formula (1-9), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is8Is n-hexyl;
formula (1-11-1): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are both n-hexyl;
formula (1-11-2): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is10Is n-hexyl;
formula (1-11-3): in the formula (1-11), Z is C, A 'is a group A' -1, R2Is absent, R1Are all made of
And R is8Is n-hexyl.
19. A method of preparing a polya-fused ring conjugated macromolecule of any of claims 13-18, comprising:
subjecting a compound represented by the following formula (2) and a compound represented by the formula (a') to a dehydration condensation reaction in the presence of a basic compound and in an organic solvent to obtain a compound represented by the formula (1); wherein the content of the first and second substances,
formula (2)
Formula (a')
20. The method of claim 19, wherein the molar ratio of the compound of formula (2) to the compound of formula (a') is 1: 2-100.
21. The method of claim 19 or 20, wherein the conditions of the dehydration condensation reaction comprise: the temperature is 20-100 deg.C, and the time is 10min-48 h.
22. The method of claim 19, wherein the basic compound is one or more of piperidine, pyridine, and triethylamine.
23. The method according to claim 22, wherein the basic compound is used in an amount of 0.1 to 1000mmol relative to 1mmol of the compound represented by formula (2).
24. The method of claim 22, wherein the organic solvent is chloroform and/or dichloromethane.
25. A photovoltaic material comprising one or more of the polya-fused ring conjugated macromolecules of any one of claims 1-6 and 13-18.
26. A solar cell comprising a light-trapping active layer, wherein an electron donor material and/or an electron acceptor material in the light-trapping active layer comprises one or more of the multiple-fused-ring conjugated macromolecules of any one of claims 1-6 and 13-18.
27. A method of producing a solar cell, wherein the method comprises using an electron donor material and/or an electron acceptor material comprising one or more of the multiple fused ring conjugated macromolecules of any one of claims 1-6 and 13-18 to form a light trapping active layer.
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